JPH1129635A - Polyol and its production and production of polyurethane resin with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyol useful as a raw material for polyurethane resins and further as a raw material for epoxy resins, polyester resins, etc., by subjecting an active hydrogen compound containing a prescribed amount of a specific polyphenylenepolyamine to the addition reaction of an alkylene oxide. SOLUTION: This polyol is obtained by reacting a methylene-crosslinked polyphenylenepolyamine containing a triaminodiphenylmethane with an alkylene oxide in the presence of a basic catalyst at a pressure of 6 kgf/cm<2> at 60-130 deg.C. The methylene-crosslinked polyphenylenepolyamine is obtained by reacting aniline with formaldehyde in the presence of an acid catalyst at 5-30 deg.C, adding an aromatic diamine to the reaction product at 15-35 deg.C, subjecting the reaction product to a rearrangement reaction at 40-110 deg.C for 1-6 hr, cooling the reaction product, adding 1-30 wt.% of an alkaline aqueous solution, neutralizing the reaction product at 30-90 deg.C for 30 min to 3 hr, and subsequently removing the salt and the organic layer. The polyol has a hydroxyl value of 17-600 mgKOH/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyol and a method for producing the same, and a method for producing a polyurethane resin using the same. More specifically, under specific reaction conditions, an active hydrogen compound containing 30 to 100% by weight of a methylene-crosslinked polyphenylene polyamine containing 40 to 99.9% by weight of triaminodiphenylmethane has a hydroxyl value of 10 to 700 mgKOH / g to which an alkylene oxide is added. Is a polyol. Furthermore, the polyol is used in an amount of 2 to 100.
The present invention relates to a method for producing a polyurethane resin obtained by reacting a polyol composition containing by weight% with a polyisocyanate compound. Polyols are used as raw materials for polyurethane resins such as polyurethane foams, polyurethane elastomers, sealing materials, flooring materials and paints, and as raw materials for resins other than polyurethane such as epoxy and polyester.

[0002]

2. Description of the Related Art Polyurethane resins are usually produced by reacting a polyol and a polyisocyanate compound in the presence of auxiliaries such as a catalyst, a foam stabilizer and a foaming agent according to the purpose. Polyurethane resin is one of the few polymer materials whose density can be adjusted to about 0.025 to about 1.3 g / cm ³ by using a foaming agent, and is used in various fields such as vehicles, furniture, clothing, heat insulating materials and civil engineering and construction. ing.
In particular, for polyurethane resins used in the foam and elastomer fields, mechanical properties are an important factor,
Various polyols have been conventionally proposed for the purpose of improving mechanical properties such as hardness and elastic modulus. Tokuhei 1-22
No. 845 discloses an aromatic amine compound which is a precursor of a polyisocyanate compound to improve the compatibility between a polyether polyol and a polyisocyanate compound, and to obtain a polyurethane foam having excellent foam appearance and thermal conductivity. Polyols containing tolylenediamine as a main component of an initiator have been proposed. However, the rigid polyurethane foam using a polyol having tolylenediamine as an initiator exemplified in this publication has insufficient wet heat dimensional stability expected by the present inventors (as exemplified in Comparative Example 3 of the present application). ).

Japanese Patent Application Laid-Open No. 2-196826 discloses 2,
Polyether polyol obtained by using 3-toluenediamine, 3,4-toluenediamine or a mixture thereof as an initiator, adding a specific amount of ethylene oxide without a catalyst, and then adding propylene oxide in the presence of an alkali metal hydroxide Is disclosed. It is described that by using the polyol, freon, which is a substance causing ozone layer destruction, can be reduced. However, there is no description about the polyol using the triaminodiphenylmethanes of the present invention.

By using an aromatic diamine, which is a precursor of a polyisocyanate compound, as a polyol initiator, the physical properties such as the surface state of the obtained foam, dimensional stability under wet heat, and thermal conductivity are improved. Is known. However, the number of active hydrogens per aromatic amine molecule is 4 for both tolylenediamine and diphenylmethanediamine, and the average number of functional groups of the polyol after alkylene oxide addition is limited.

JP-B-49-14746 discloses the preparation of a methylene-bridged polyphenylenepolyamine containing triaminodiphenylmethane having two aromatic rings and three secondary amino groups per molecule, that is, six active hydrogens. A method is disclosed. The publication describes a polymethylene polyphenyl polyisocyanate obtained by phosgenating the polyamine, but does not describe a polyol obtained by adding an alkylene oxide to the polyamine.

JP-A-52-87149 teaches a method for producing an asymmetric polyamine in the presence of an aromatic amine, formaldehyde and an acid catalyst. However, in this method, an asymmetric polyamine and a symmetric polyamine are obtained as a mixture, and since the second amine is an aromatic monoamine, the resulting asymmetric polyamine is mainly composed of diamine, and triaminodiphenylmethane is selected. Generation is not disclosed. It is also described that when an amine containing an aromatic diamine, 4-amino-4′-methylamino-diphenylmethane, is added to a polyol used for foaming, the compressive strength of a flexible polyurethane foam made from toluene diisocyanate gradually increases. However, it does not disclose a polyol obtained by adding an alkylene oxide to the compound.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyol for producing a polyurethane resin having excellent mechanical properties and appearance, and a method for producing the same.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an active hydrogen compound containing a specific amount of a methylene-bridged polyphenylenepolyamine containing triaminodiphenylmethane under specific reaction conditions. ,
Hydroxyl value to which alkylene oxide is added is 10 to 70
The inventors have found that the above object can be achieved by producing a polyurethane resin by reacting a polyol composition containing a specific amount of 0 mgKOHg of a polyol with a polyisocyanate compound, and completed the present invention.

That is, a first object of the present invention is an alkylene oxide adduct of methylene-bridged polyphenylenepolyamine containing triaminodiphenylmethane, and a polyol having a hydroxyl value of 10 to 700 mgKOH / g. A second object of the present invention is to provide an active hydrogen compound containing methylene-bridged polyphenylenepolyamine containing 40 to 99.9% by weight of triaminodiphenylmethane in the presence of a basic catalyst in the presence of a basic catalyst at a reaction temperature of 4 to 100% by weight.
0 to 150 ° C., maximum reaction pressure 10 kgf / cm ² (98
(1) A method for producing a polyol of the first object of the present invention, wherein the addition polymerization of an alkylene oxide is carried out under the condition of 0 kPa). A third object of the present invention is a method for producing a polyurethane resin, comprising reacting a polyol composition containing 2 to 100% by weight of the polyol obtained for the first object with a polyisocyanate compound.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a methylene-crosslinked polyphenylenepolyamine containing triaminodiphenylmethane used in the present invention will be described. As the triaminodiphenylmethane of the present invention, compounds having various structures can be obtained depending on the type of aromatic amine used in the reaction. The triaminodiphenylmethane of the present invention indicates a compound having two aromatic rings and three amino groups in one molecule. For example, 4,4 ',
6-triamino-3-methyldiphenylmethane, 2,
4,4'-triamino-3-methyldiphenylmethane can be exemplified. When synthesizing triaminodiphenylmethane, a condensate of an aromatic amine and formaldehyde is generated. In the present invention, a compound having three or more aromatic rings in one molecule and a methylene-bonded aromatic ring is defined as a methylene-bridged polyphenylenepolyamine. Usually, an aqueous formaldehyde solution is added to aniline in the presence of an acid catalyst to carry out a condensation reaction, and then an aromatic diamine is continuously added at 0 to 40 ° C. without isolating the condensation reaction product. The rearrangement reaction temperature after the addition of the aromatic diamine is not lower than the temperature at the time of addition of the aromatic diamine and less than 150 ° C. After the rearrangement reaction, the acid catalyst is neutralized with an aqueous alkaline solution, separated and removed, and subjected to a method such as distillation under reduced pressure. Methylene-crosslinked polyphenylenepolyamine containing triaminodiphenylmethane, which is a product, is produced.

In the initial reaction of the present invention, an acid catalyst and formaldehyde are added to aniline, and the reaction is carried out at 0 to 40 ° C., preferably 5 to 40 ° C.
Perform in the range of 30 ° C. The rearrangement reaction of the condensate proceeds slightly, even at around room temperature. To increase the selectivity of triaminodiphenylmethane, formaldehyde is added at as low a temperature as possible. The amount of aniline used is 1.0 to 5.0 mol, preferably 1.5 to 5.0 mol, per 1 mol of formaldehyde. If the amount is less than 1.0 mol, a large amount of condensation intermediate is precipitated, and the yield of the target substance is reduced. If it exceeds 5.0 moles, the amount of unreacted aniline increases. Formaldehyde is preferably in the form of an aqueous solution. Although the concentration of formaldehyde is not particularly limited, it is usually used in a formaldehyde aqueous solution of 20 to 40% by weight.

As the acid catalyst, at least one acid selected from inorganic or organic acids is used. For example, hydrochloric acid,
Mineral acids such as phosphoric acid, sulfuric acid, nitric acid, or acetic acid, oxalic acid,
Succinic acid, phthalic acid, maleic acid, methanesulfonic acid,
Organic acids such as p-toluenesulfonic acid, furthermore, trifluoromethanesulfonic acid, Nafion H (Dupon
and t). The most preferred of these acids are hydrochloric acid and oxalic acid. The amount of the acid catalyst used is 0.0 to the total number of moles of aniline and aromatic diamine.
It is 1 to 2 moles, preferably 0.03 to 0.5 moles.

After the addition of formaldehyde,
The aromatic diamine is added at a temperature of 0 ° C, preferably 15-35 ° C. At this time, in order to improve the selectivity of triaminodiphenylmethane, it is preferable to add it at as low a temperature as possible. However, when the temperature is lower than 0 ° C., the solubility of the aromatic diamine is extremely reduced, and the reaction time is prolonged. On the other hand, when the temperature exceeds 40 ° C., the selectivity of triaminodiphenylmethane decreases. After the addition of the aromatic diamine, usually 30 to
The rearrangement reaction is performed at 150 ° C., preferably at 40 to 110 ° C. for 1 to 6 hours. After cooling, the acid catalyst is neutralized with an alkaline aqueous solution to obtain a crude product.

The aromatic diamine used in the present invention includes:
o-phenylenediamine, m-phenylenediamine, p
-Phenylenediamine and 2-chlorophenylene-
1,3-diamine, 4-bromophenylene-1,3-diamine, 2-methoxyphenylene-1,4-diamine,
3-ethoxyphenylene-1,2-diamine, 4-hexyloxyphenylene-1,2-diamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 2,3-tolylenediamine, 3,4 -Tolylenediamine, 1,2-
Xylene-4,5-diamine, 2-ethylphenylene-
1,4-diamine, 2-hexylphenylene-1,4-
Diamine, di (4-aminophenyl) methane, 4,4 '
-Diaminodiphenylmethane and the like. These aromatic diamines can be used as a mixture. Among these, preferred aromatic diamines are 2,4-tolylenediamine, 2,6-tolylenediamine and m-phenylenediamine. The amount of these aromatic diamines used is 0.3 to 1.
5 mol, preferably 0.3 to 1.0 mol.

As the alkaline aqueous solution for neutralizing the acid catalyst, for example, an aqueous solution prepared by adjusting sodium hydroxide, potassium hydroxide, ammonia or the like to an aqueous solution of 1 to 30% by weight can be used. The neutralization reaction conditions are not particularly limited, but the reaction is usually performed at 30 to 90 ° C. for 30 minutes to 3 hours. After the neutralization reaction, the liquid is allowed to stand still to remove salts from the reaction system. Thereafter, the organic layer is subjected to distillation under reduced pressure or the like to obtain a methylene-crosslinked polyphenylenepolyamine containing triaminodiphenylmethane.

In producing the methylene-crosslinked polyphenylenepolyamine containing triaminodiphenylmethane of the present invention, a solvent can be used as long as the reaction is not inhibited. Examples of such a solvent include aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; chlorinated hydrocarbons such as monochlorobenzene and orthodichlorobenzene;
Esters such as butyl and isoamyl acetate are exemplified. After completion of the reaction, the solvent is removed by a method such as distillation under reduced pressure. The recovered solvent can be reused for the purpose of improving economy.

Next, the polyol will be described. Triaminodiphenylmethane contained in the methylene-crosslinked polyphenylenepolyamine of the present invention is 40 to 99.9% by weight.
It is. When the content of triaminodiphenylmethane contained in the methylene-crosslinked polyphenylenepolyamine is less than 40% by weight, the mechanical properties of the urethane resin using the polyol after the addition of the alkylene oxide are reduced. On the other hand, when the content of triaminodiphenylmethane in the methylene-crosslinked polyphenylenepolyamine is more than 99.9% by weight, the cost for purification becomes large, and the economical efficiency is deteriorated.

The triaminodiphenylmethane of the present invention is
The hydroxyl value (hereinafter abbreviated as OHV) of the polyol after addition of the alkylene oxide to the methylene-crosslinked polyphenylenepolyamine containing 0 to 99.9% by weight is 10 to 7.
00 mg KOH / g is preferred. More preferably, 15
６650 mg KOH / g, most preferably 17-60
0 mgKOH / g. OHV is 10mgKOH / g
When it is less than the above range, the effect of modifying the polyurethane resin by the polyamine of the present invention is reduced. OHV is 700mgKOH
/ G, the viscosity of the polyol increases and the miscibility with the polyisocyanate compound decreases. When the polyol of the present invention is used in the field of flexible polyurethane foam, it is preferable to use one having a low OHV in the above range, and when using the polyol in the field of rigid polyurethane foam, it is preferable to use one having a high OHV in the above range. When used in the field of non-foamed polyurethane resin, the OHV of the polyol to be used is selected according to the field of application of the polyurethane resin. Further, the polyol of the present invention obtained by adding an alkylene oxide to the methylene-crosslinked polyphenylenepolyamine can be used as a crosslinking agent that reacts with an isocyanate group when producing a polyurethane resin such as a polyurethane foam, an elastomer, a floor material, and an elastic fiber. When the polyol of the present invention is used as a crosslinking agent, its OHV is preferably from 100 to 700 mgKOH / g.

When the purity of triaminodiphenylmethane in the methylene-crosslinked polyphenylenepolyamine is relatively high, the polyamine and the active hydrogen compound can be used in combination for the purpose of reducing the load on the stirrer during the alkylene oxide reaction. The amount of the methylene-crosslinked polyphenylenepolyamine containing triaminodiphenylmethane of the present invention is from 30 to 10 based on 100 parts by weight of the active hydrogen compound.
0% by weight is preferred. More preferably, it is 40 to 100% by weight, most preferably 50 to 100% by weight. When the amount of the polyamine of the present invention is less than 30% by weight, the effect of modifying the polyurethane resin with triaminodiphenylmethane is reduced. Active hydrogen compounds that can be used in combination with methylene-crosslinked polyphenylene polyamine include, for example, water,
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,
3-butanediol, 1,4-butanediol, 1,6
Dihydric alcohols such as hexanediol and 1,4-cyclohexanediol, alkanolamines such as monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, triethanolamine and triisopropanolamine, glycerin, diglycerin, triglycol Polyhydric alcohols such as methylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol; sugars such as glucose, sorbitol, dextrose, fructose, sucrose, and methyl glucoside or derivatives thereof; ethylenediamine, di (2-aminoethyl) amine; Fatty acid amines such as hexamethylenediamine, tolylenediamine,
Examples include aromatic amines such as diphenylmethanediamine, and phenol compounds such as bisphenol A, bisphenol F, bisphenol S, novolak, resol, hydroquinone, and resorcin. These active hydrogen compounds can be used in combination of two or more.

The reaction conditions for the reaction of the alkylene oxide with the methylene-bridged polyphenylenepolyamine containing triaminodiphenylmethane include a reaction temperature of 40 to 150 ° C., preferably 60 to 130 ° C. in the presence of a basic catalyst. When the reaction temperature is lower than 40 ° C., the reaction time of the alkylene oxide becomes longer. When the reaction temperature is higher than 150 ° C., side reactions of propylene oxide increase. The reaction is performed at a maximum pressure of 10 kgf / cm ² (980 kPa). More preferably, 7 kgf / cm ² (686 kP
a), most preferably 6 kgf / cm ² (588 kP
a). The reaction maximum pressure is 10 kgf / cm ² (98
When the pressure is higher than 0 kPa), the side reaction of propylene oxide increases. Further, a solvent may be used as long as the polymerization reaction is not inhibited. Examples of such a solvent include aliphatic hydrocarbons such as pentane, hexane, and peptane; ethers such as diethyl ether, tetrahydrofuran, and dioxane; dimethyl sulfoxide;
Aprotic polar solvents such as dimethylformamide. When a solvent is used, a method of recovering and reusing the solvent after the production is desirable in order not to increase the production cost of the polyol.

Examples of the alkylene oxide used in the present invention include propylene oxide, ethylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether and the like. These may be used in combination of two or more. Of these, preferably propylene oxide,
Butylene oxide, ethylene oxide, and styrene oxide. As a polymerization method, in the case of propylene oxide and ethylene oxide, for example, after polymerization of propylene oxide, an ethylene oxide cap reaction in which ethylene oxide is copolymerized in a block, or after polymerization of ethylene oxide, propylene oxide is copolymerized in a block. A propylene oxide cap reaction, a random reaction of randomly copolymerizing propylene oxide and ethylene oxide, and further polymerizing ethylene oxide after propylene oxide polymerization,
Next, a triblock copolymerization reaction in which propylene oxide is polymerized, or a triblock copolymerization reaction in which propylene oxide is polymerized after ethylene oxide polymerization and then ethylene oxide is polymerized.

At the time of the alkylene oxide addition reaction, a basic catalyst is used. However, there are the following two methods for charging the catalyst. (A) A method in which a catalyst is added simultaneously with methylene-crosslinked polyphenylenepolyamine to carry out an addition reaction of alkylene oxide (hereinafter, abbreviated as a batch addition method). (B) A method of reacting 0.3 to 4.0 mol of alkylene oxide per equivalent of amino group of methylene-crosslinked polyphenylene polyamine without a catalyst, adding a catalyst, and further performing an addition reaction of the alkylene oxide ( Hereinafter, it is abbreviated as a post-addition method). In addition polymerization of the alkylene oxide to the methylene-crosslinked polyphenylenepolyamine of the present invention, any of the above methods may be used depending on the field of use of the polyol. Usually, for polyols used in the foam field, method (b) is preferred.

Examples of the basic catalyst used in the addition reaction of the alkylene oxide include alkali metals, alkaline earth metals and an amine compound. Examples of the alkali metals and alkaline earth metals include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide. And alkali metal or alkaline earth metal hydroxides such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate and barium carbonate. And hydrogen carbonates such as potassium hydrogen carbonate, sodium hydrogen carbonate and cesium hydrogen carbonate. Examples of the amine compound include triethylamine, dimethylethanolamine, pyridine, methyldiethylamine, tri-n-propylamine, dimethylpalmitylamine, and dimethyloctylamine. These catalysts can be used alone or in combination of two or more.

The polyol obtained by the method of the present invention, when a solvent is used for the addition reaction, is simply removed,
In some cases, it can be used as a raw material for a polyurethane resin as it is. Usually, inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, formic acid,
Acetic acid, oxalic acid, succinic acid, phthalic acid, organic acids such as maleic acid, a method of treating with at least one kind of neutralizing agent selected from carbon dioxide, a method of treating with an ion exchange resin, and Tomix AD series, for example, Tomix AD-600, Tomix AD-700 (manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoword series, for example, Kyoword 3
00, Kyoword 400, Kyoword 500, Kyoword 600, Kyoword 700, Kyoword 2
000 (manufactured by Kyowa Chemical Industry), MAGNESOL (DAL
The product is treated with an adsorbent commercially available under various trade names such as LAS, or a method using a combination of the above-described neutralization treatment and the adsorbent to remove the basic catalyst before use.
Further, it can also be used after purifying the polyol using water, a solvent inert to the polyol, or a mixture thereof.

For the purpose of stabilizing the quality of the polyol,
After the above-mentioned purification treatment, an antioxidant such as t-butylhydroxytoluene (BHT) may be added. The antioxidant is usually added to 10 parts by weight of the polyol.
Use 0 to 5000 ppm.

Next, a method for producing the polyurethane resin of the present invention will be described. A polyurethane resin is produced by reacting a polyisocyanate compound with a polyol composition containing 2 to 100 parts by weight of the polyol obtained by the above-described method. Examples of the polyol that can be used together with the polyol of the present invention include polyols obtained by adding an alkylene oxide to an active hydrogen compound such as an alcohol, a phenol compound, a polyamine, or an alkanolamine by the method described above. As the active hydrogen compound, the compounds described above are used. These active hydrogen compounds can be used in combination of two or more. Furthermore, polyols such as polymer-dispersed polyols, polyester polyols, polytetramethylene glycol, polycarbonate polyols and polybutadiene-based polyols obtained by a conventionally known production method can also be used. The hydroxyl value of these polyols is from 10 to 700 mgKOH / g.
Preferably, it is 15 to 600 mgKOH / g. Of the polyurethane foams, it is preferable to use a high polyurethane foam having a high OHV and a low polyurethane foam having a low OHV.

The polyisocyanate compound for producing the polyurethane resin of the present invention is used for producing aromatic, aliphatic, alicyclic and other polyurethanes having two or more isocyanate groups in one molecule. Known ones can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 /
20), isomer mixture in 65/35 weight ratio (TDI-65 / 35), crude tolylene diisocyanate containing polyfunctional tar (polyfunctional tar is a by-product of isocyanate production, Group in the molecule
It is a mixture of tar-like substances containing more than one. same as below. ), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate,
2,2′-diphenylmethane diisocyanate, any isomer mixture of diphenylmethane diisocyanate, 3
Crude diphenylmethane diisocyanate (polymeric MDI) containing core or higher polyfunctional tar, toluylene diisocyanate, xylylene diisocyanate,
1-methyl-2,4-diisocyanatecyclohexane, 1-methyl-2,6-diisocyanatecyclohexane, bis (4-isocyanatocyclohexyl) methane and isomers thereof, hexamethylene diisocyanate, isophorone diisocyanate, naphthalenediisocyanate, paraphenylene diisocyanate, Examples include methylene-bridged polyphenylene polyisocyanate obtained by phosgenation of norbornene diisocyanate and methylene-bridged polyphenylene polyamine containing triaminodiphenylmethane obtained in the present invention. Carbodiimide-modified, buret-modified, allophanate-modified, uretminin-modified, urea-modified products of these polyisocyanates, or prepolymers obtained by modifying these polyisocyanates with polyols or monools alone or in combination thereof Is mentioned. The above polyisocyanate compounds can be used in a mixture at an arbitrary ratio. Particularly preferably, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
80/20 weight ratio of these organic polyisocyanates (T
DI-80 / 20), 65/35 weight ratio (TDI-65
/ 35), 4,4′-diphenylmethane diisocyanate and modified products thereof, Polymeric MD
I, a mixture of the above-mentioned tolylene diisocyanate and polymeric MDI, a methylene-crosslinked polyphenylene polyisocyanate obtained by phosgenating a methylene-crosslinked polyphenylene polyamine containing isophorone diisocyanate, norbornene diisocyanate and the triaminodiphenylmethanes obtained in the present invention. is there.

The above-mentioned polyol composition is reacted with a polyisocyanate compound in the presence of a foaming agent such as water, a foam stabilizer such as an organosilicon surfactant, a catalyst, and other auxiliaries to form a polyurethane foam or an elastomer. It can be used as a raw material for polyurethane resins such as sealing materials, paints, adhesives, waterproofing materials, flooring materials, and elastic fibers.

First, a method for producing a polyurethane foam will be described. The polyol composition used as a raw material of the polyurethane resin of the present invention is a polyol having a methylene-crosslinked polyphenylpolyamine containing triaminodiphenylmethanediamine of the present invention as an initiator, and 2 to 100 parts by weight of 100 parts by weight of the polyol composition. Occupies preferably 10 to 85 parts by weight, more preferably 20 to 70 parts by weight. If the amount of the polyol of the present invention is less than 2 parts by weight based on 100 parts by weight of the polyol, the compatibility of the triaminodiphenylmethane with the polyisocyanate compound becomes low.

The foaming agent used for producing a polyurethane foam is slightly different between a flexible polyurethane foam and a rigid polyurethane foam. In the case of producing a flexible polyurethane foam, water alone may be used as a foaming agent, but in the case of producing a rigid polyurethane foam, water, a low-boiling hydrocarbon-based compound, a hydrochlorofluorocarbon, (Hereinafter HC
Abbreviated as FC. ), Hydrofluorocarbon (hereinafter abbreviated as HFC), fluorocarbon (hereinafter, abbreviated as HFC)
Abbreviated as FC. ) Or fluorinated ethers. Examples of the low-boiling hydrocarbon compound include cyclopentane, n-pentane, and isopentane. HCFCs include HCFC
HFC-134a, HFC
-356 or HFC-245fa, and examples of the FC compound include C ₅ F _12. As the fluorinated ethers, compounds described in JP-A-4-28729 can be used. When the blowing agent is water alone, it is used in an amount of 1 to 9 parts by weight based on 100 parts by weight of the polyol composition containing the polyol of the present invention. Low boiling hydrocarbon compounds, H
When at least one blowing agent selected from CFCs, HFCs, FCs and fluorinated ethers is used, the polyol composition 100 containing the polyol of the present invention is used.
Use 1 to 40 parts by weight with respect to parts by weight.

As the polyisocyanate compound used in the present invention, the aforementioned polyisocyanate compounds are used. Usually, the ratio of the concentration of isocyanate groups in the polyisocyanate compound to the concentration of active hydrogen groups in the active hydrogen compound (hereinafter, abbreviated as NCO index) is 0.7 to 0.7.
The amount used of the polyisocyanate compound is determined by adjusting the amount to 1.8, preferably 0.8 to 1.5.

As the catalyst, a conventionally known catalyst for producing a polyurethane such as an amine compound or an organometallic compound can be used. Examples of the amine compound include, for example, triethylamine, tripropylamine, tributylamine, N,
Organics such as N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine, and salts of triethylenediamine Examples of the metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. No. These catalysts can be used alone, but usually two or more kinds are used in combination. The amount of the catalyst used is 0.0001 to 1 with respect to 100 parts by weight of the polyol composition.
0.0 parts by weight.

When producing a polyurethane foam,
A foam stabilizer is required. As the foam stabilizer, a conventionally known organic silicon-based surfactant can be used. For example, L-520, L-532, L-540, L-54 manufactured by Nippon Unicar Co., Ltd.
4, L-550, L-3600, L-3601, L-5
305, L-5307, L-5309, etc., SRX-253, SRX-274C, S manufactured by Dow Corning Toray Co., Ltd.
F-2961, SF-2962, F-114, F-121, F-122, F-220 manufactured by Shin-Etsu Silicone Co., Ltd.
F-230, F-258, F-260B, F-317,
Examples include F-341, F-601, and F-606, and TFA-420 and TFA-4202 manufactured by Toshiba Silicone Co., Ltd. These foam stabilizers can be arbitrarily mixed and used, and the amount is 0.05 to 10 parts by weight based on 100 parts by weight of the polyol composition.

When producing a flexible polyurethane foam, a crosslinking agent is usually used. Examples of the crosslinking agent include dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, and 1,4-butanediol;
Alkanolamines such as triethanolamine, diethanolamine and monoethanolamine; aliphatic amine compounds such as ethylenediamine, diethylenetriamine and triethylenetetramine; aromatics such as aniline, 2,4-tolylenediamine and 2,6-tolylenediamine OHV200 obtained by adding an aromatic alcohol such as amine, hydroquinone, resorcinol, novolak, and resol, and an alkylene oxide such as propylene oxide and ethylene oxide to these active hydrogen compounds.
800 mg KOH / g polyol. Further, the polyol of the present invention can be used as a crosslinking agent.

A flame retardant is used depending on the purpose of use of the polyurethane foam. Tris (2-chloropropyl) phosphate, tris (dichloropropyl) as flame retardant
Phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, CR-50 manufactured by Daihachi Chemical Co.
5 and CR-507, Phos from Monsanto Chemical
agard 2XC-20 and C-22-R, and Fyroll-6 manufactured by Stoffer Chemical Co., Ltd., and the amount of the polyol composition is 100%.
0.1 to 30 parts by weight, preferably 0.2 to 30 parts by weight
-20 parts by weight.

A plasticizer, a coloring agent, an antioxidant, an anti-scorch agent and the like can be added to the polyol composition according to the purpose.

For the polyurethane foam, a liquid (hereinafter, abbreviated as “resin premix”) prepared by mixing predetermined amounts of the above-mentioned auxiliary agents such as the polyol, the foaming agent, the catalyst, the foam stabilizer and the cross-linking agent is prepared, and the predetermined temperature is obtained. For example, the temperature is adjusted in the range of 20 to 30 ° C. A predetermined amount of the polyisocyanate compound is measured and adjusted to a predetermined temperature, for example, a range of 20 to 30 ° C. Usually, the amount of the polyisocyanate compound used is calculated by the NCO index. Thereafter, the resin premix and the polyisocyanate compound are rapidly mixed, and the resin premix and the polyisocyanate compound are injected directly into a mold whose temperature is adjusted to a predetermined temperature, for example, 20 to 70 ° C. A polyurethane foam is produced by a method of spraying and molding a mixture with an isocyanate compound.

The polyurethane resin other than the polyurethane foam, such as elastomer and sealing, will be described. The following two methods can be used to produce these polyurethane resins. (C) A method of simultaneously mixing and molding a polyol composition containing the polyol of the present invention, a polyisocyanate compound and a chain extender (hereinafter abbreviated as a one-shot method). (D) a method of reacting a polyol composition containing the polyol of the present invention with a polyisocyanate compound to synthesize a prepolymer having an isocyanate group at a molecular terminal, and reacting the prepolymer with a chain extender to form a prepolymer (hereinafter, referred to as a molding method). Abbreviated as prepolymer method). When the OHV of the polyol of the present invention is high in the above range, the method (c) is preferable, and when the OHV is low, the method (d) is preferable.

First, the one-shot method (c) will be described. The polyol used in the one-shot method is the same as the polyol composition described above. During the production of urethane foam, polyoxyalkylene polyol or polymer-dispersed polyol is preferably used,
For the production of polyurethane resins other than foams, all the polyols described above can be used. However, for example, since the polyester polyol and the polytetramethylene glycol become incompatible depending on the mixing ratio, the appearance of the mixture may become cloudy. The mixing of the polyols is carried out after understanding the chemical and physical properties of each.

As the polyisocyanate compound, the polyisocyanate compound described in the method for producing a urethane foam exemplified above is used. The chain extender is a compound having two or more active hydrogen groups capable of reacting with an isocyanate group in one molecule, and at least one of a polyol compound and a polyamine compound is used. Examples of the polyol compound include dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol; glycerin; It contains trihydric alcohols such as methylolpropane, cyclohexylene such as cyclohexanediol and spirohexanediol, a spiro ring and a methylene chain, and includes various bonds such as an ether bond and an ester bond as those linking them. Derivatives containing various substituents can be used. Further, as the polyamine compound, tolylenediamine, 3,5-diethyl-2,4-diaminotoluene,
3,5-diethyl-2,6-diaminotoluene, diphenylmethanediamine, m-phenylenediamine, 3,
Aromatic diamines such as 3′-dichloro-4,4′-diaminodiphenylmethane and diethyltoluenediamine;
Conventionally known polyamine compounds such as aliphatic, alicyclic diamines such as isophorone diamine and norbornene diamine, linear aliphatic diamines, alkyl dihydrazides such as carbodihydrazide and adipic dihydrazide, and derivatives thereof can be used. Further, polyols obtained by adding an alkylene oxide to these active hydrogen compounds by a conventionally known method can also be used as a chain extender.

The above-mentioned polyol, polyisocyanate compound and chain extender are rapidly mixed, subjected to defoaming under reduced pressure, and poured into a mold heated to a predetermined temperature, for example, 40 to 130 ° C. to prepare a molded product. At this time, a curing catalyst, a filler, a plasticizer, a dye / pigment, a reinforcing agent, a flame retardant, a stabilizer and the like can be used according to the purpose. The catalyst described above can be used as the polyurethane curing catalyst. The amount used is 0.01 to 4.0 parts by weight, preferably 0.1 part by weight, per 100 parts by weight of the polyol composition containing the polyol of the present invention.
03 to 2.0 parts by weight.

As the filler, fumed silica, silica, silicic anhydride, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, talc, titanium oxide, bentonite, ferric oxide, hydrogenated castor oil,
Zinc stearate and the like can be mentioned, and the addition amount thereof is 2 to 60 parts by weight, preferably 10 to 50 parts by weight based on 100 parts by weight of the polyol composition containing the polyol of the present invention.

As the plasticizer, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, butyl benzyl phthalate, butyl phthalyl butyl glycolate,
Dioctyl sebacate, tricresyl phosphate, tributyl phosphate, chlorinated paraffin, petroleum ether, and the like, the amount of which is 1 to 40 parts by weight, preferably 100 parts by weight of the polyol composition containing the polyol of the present invention, preferably 5 to 15 parts by weight.

Examples of the reinforcing agent include black filler carbon black, white filler white carbon, silica, silicate kaolin, bentonite, anhydrous fine silica, barite, gypsum, bone powder, dolomite, and the like. Is from 1 to 50 parts by weight, preferably from 2 to 30 parts by weight, based on 100 parts by weight of the polyol composition containing the polyol of the present invention.

As the flame retardant, the compounds exemplified above can be used. The amount used is 0.05 to 30 parts by weight, preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the polyol composition containing the polyol of the present invention.

Examples of the stabilizer include an antioxidant, an ultraviolet absorber, a heat stabilizer and the like. The antioxidant is not particularly limited. For example, butylhydroxyanisole, t
-Butylhydroxytoluene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-
Hydroxybenzyl) benzene, 3,9-bis [2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl]
-2,4,8,10-tetraoxaspiro (5,5) undecane, distearylthiodipropionate and the like. Examples of the ultraviolet absorber include pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. As a heat stabilizer, Tris (2, 4
-Di-t-butylphenyl) phosphite, triphenyl phosphite, trilauryl phosphite and the like. These addition amounts are 100 to 80 parts by weight with respect to 100 parts by weight of the polyol composition containing the polyol of the present invention.
00 ppm is preferred. Pigment according to the present invention,
The above-mentioned organic solvents, moisture removing agents, and the like can be used.

Next, the prepolymer method (d) will be described. As the polyisocyanate compound used in the present invention, the compounds exemplified above are used. Prepolymer (hereinafter,
It is called an isocyanate group-terminated prepolymer. )), The NCO index is from 1.3 to 20.0,
Preferably 1.4 to 12.0, more preferably 1.5
９9.0.

The isocyanate group-terminated prepolymer has a free isocyanate group content (hereinafter abbreviated as NCO%) of 0.1 to 40.0% by weight, preferably 0.3% by weight.
~ 25.0% by weight, more preferably 0.4 ~ 18.0.
% By weight. The isocyanate group-terminated prepolymer used in the one-pack type curable composition obtained by using water in the air as a curing agent has a low NCO% and glycols such as 1,4-butanediol and polyoxyalkylene polyol; The isocyanate group-terminated prepolymer used in a two-part curable composition using a polyamine compound such as'-dichloro-4,4'-diaminodiphenylmethane as a curing agent has a higher NCO% than that of a one-part type. You.

The temperature for producing the isocyanate group-terminated prepolymer is preferably from 50 to 120 ° C. Particularly preferably, it is 70 to 105 ° C. At the time of the reaction, it is desirable to carry out the reaction in the presence of an inert gas in order to avoid contact with moisture in the air. Examples of the inert gas include nitrogen and helium, and nitrogen is preferable. The reaction is carried out with stirring under a nitrogen atmosphere for 2 to 20 hours. A catalyst may not be used, but when it is used, the above-mentioned amine compound or organometallic compound can be used. These catalysts can be arbitrarily mixed and used. Among these catalysts,
Organometallic catalysts are preferred, and the amount used is based on 100 parts by weight of the polyol composition containing the polyol of the present invention.
0.0001 to 2.0 parts by weight, preferably 0.01 to
1.0 part by weight.

When producing the isocyanate group-terminated prepolymer, an organic solvent which is inert to the polyisocyanate compound or the polyol before or after the reaction can be used. The amount of the organic solvent is at most 40% by weight, preferably at most 20% by weight, based on the total weight of the polyol and the polyisocyanate compound. As such a solvent, aromatic, aliphatic, alicyclic, ketone, ester and ester ether solvents can be used. For example,
Toluene, xylenes, hexanes, cyclohexane,
Methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and the like.

The isocyanate group-terminated prepolymer includes:
Fillers, plasticizers, flame retardants, stabilizers and the like can be blended. These auxiliaries use those described above. It is preferable that the curing catalyst is blended with the chain extender exemplified above. When molding a polyurethane resin by the prepolymer method,
To the isocyanate group-terminated prepolymer blended with an auxiliary according to the purpose, a chain extender blended with a curing catalyst according to the purpose is rapidly mixed, and the mixture is degassed under reduced pressure, and is heated to a predetermined temperature, for example, 30 to 130 ° C. Injection into a heated mold and molding,
Alternatively, it is carried out by a method of reacting an isocyanate group-terminated prepolymer applied to a substrate with moisture in the air to obtain a cured product.

[0052]

EXAMPLES Examples and comparative examples of the present invention are shown below.
Embodiments of the present invention will be clarified, but the present invention is not limited to these embodiments.

The hydroxyl value (hereinafter abbreviated as OHV: unit mgKOH / g) of the polyols of Examples and Comparative Examples is J
It was determined by the method described in IS K 1557.

Example 1 Polyol A Aniline 22 was placed in a 1-liter glass flask equipped with a thermometer, a stirrer, a nitrogen inlet and a dropping funnel.
3.2 g was charged, and 112.6 g of a 35% by weight aqueous hydrochloric acid solution was added while maintaining the temperature at 20 ° C. Subsequently, 37% by weight
81.1 g of the formalin aqueous solution was added dropwise over 30 minutes while maintaining the temperature in the range of 25 to 30 ° C. At the same temperature, 2, 4
-Tolylenediamine (manufactured by Mitsui Toatsu Chemicals, Inc.) 195.
2 g was added, and then the temperature was raised to 50 ° C.
After reacting for an hour, the temperature was further raised to 90 ° C., and the reaction was carried out at the same temperature for 1 hour. All the reactions described above were performed under a nitrogen atmosphere. Next, the mixture was cooled to 70 ° C., and 162 g of a 32% by weight aqueous sodium hydroxide solution was added. A washing operation was performed three times with 300 g of warm water at 50 ° C. to obtain 428.9 g of a crude amine. The composition of the crude amine determined by liquid chromatography (HPLC) and gas chromatography (GC) was 8.7% by weight of diaminodiphenylmethane 51.3% by weight of triaminodiphenylmethane 15.9% by weight of aniline 2,4-tolylenediamine 10.4% by weight of polynuclear polyamines was 13.7% by weight. After distilling off excess aniline, 200 ° C., 1.0
mmHgabs. The 2,4-tolylenediamine was distilled off using a thin film evaporator under the conditions of (133 Pa) to obtain a methylene-crosslinked polyphenylpolyamine containing triaminodiphenylmethanes (hereinafter abbreviated as a polyamine mixture). The composition of the polyamine mixture was 6.3% by weight of diaminodiphenylmethane, 72.9% by weight of triaminodiphenylmethane, 0.7% by weight of 2,4-tolylenediamine, and 20.1% by weight of polynuclear polyamines. The content of triaminodiphenylmethane contained in the methylene-crosslinked polyphenylpolyamine is 72.9.
% By weight. Next, a stirrer, a pressure gauge, an alkylene oxide blowing port and a nitrogen inlet were installed.
0.25 mol of triethanolamine (manufactured by Mitsui Toatsu Chemicals, Inc.) was added to 1 mol of the polyamine mixture in a liter pressure-resistant autoclave (the polyamine mixture was used in an amount of 90 to 100 parts by weight of the active hydrogen compound). 0.4% by weight), and after nitrogen replacement, stirring was performed at 100 ° C. for 1 hour. Thereafter, gauge pressure 1.2 kgf / c with nitrogen
Under the conditions of a reaction temperature of 100 ° C. and a maximum pressure of 5 kgf / cm ² (490 kPa) from a state of m ² (219 kPa), 2.5 mol of ethylene oxide is reacted with 1 equivalent of amino group in the polyamine mixture. Was. When the change in the internal pressure of the autoclave disappeared, 100 ° C,
10 mmHgabs. (1330 Pa), and a reduced pressure treatment was performed for 30 minutes. After pressurizing to atmospheric pressure with nitrogen, 0.05 mol of potassium hydroxide (in the form of a 50% by weight aqueous solution of potassium hydroxide) is added to 1 mol of the polyamine mixture, and the mixture is stirred at 100 ° C., 10 mm
Hgabs. (1330 Pa) Dehydration under reduced pressure was performed for 3 hours under the following conditions. Then, at the same temperature, 20 mmHg
abs. (2660 Pa) OHV 35
The addition reaction of propylene oxide was performed until it reached 0 mgKOH / g. The maximum reaction pressure at this time is 4 kgf / c
m ² (392 kPa). When the change in the internal pressure of the autoclave has ceased, 100 ° C., 10 mmHgab
s. (1330 Pa) under reduced pressure for 2 hours to obtain a crude polyol. After pressurizing to atmospheric pressure with nitrogen, 1 mole per 1 mole of potassium in the crude polyol
A molar aqueous oxalic acid solution (in the form of a 9 wt% aqueous oxalic acid solution) was added, and a neutralization reaction was performed at 80 ° C. for 2 hours. Then, t, which is an antioxidant, is added to 100 parts by weight of the crude polyol.
-800 ppm of butylhydroxytoluene (BHT)
And adsorbent KW-700 (manufactured by Kyowa Chemical Co., Ltd.)
Finally, 105 ° C., 10 mmHgabs. (1330 Pa), a pressure reduction treatment was performed for 3 hours. Then, the mixture was filtered under reduced pressure using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyol. The hydroxyl value of the polyol after the purification treatment was 355 mgKOH / g.

Hereinafter, a comparative example will be described. In order to clarify the effects of the methylene-bridged polyphenylene polyamine containing triaminodiphenylmethanes of the present invention, o-tolylenediamine (Comparative Example 1) and 4,4′-diphenylmethanediamine (Comparative Example 2) were used as aromatic amine compounds. Was used to synthesize a polyol.

Comparative Example 1 Polyol B An o-tolylenediamine (Mitsui Toatsu Chemical Co., Ltd.) was placed in a 1-liter pressure-resistant autoclave equipped with a stirrer, a pressure gauge, an alkylene oxide blowing port and a nitrogen inlet.
0.25 mol of triethanolamine (manufactured by Mitsui Toatsu Chemicals, Inc.) per 1 mol of o-tolylenediamine was used in an amount of 7 parts per 100 parts by weight of the active hydrogen compound.
6.6% by weight), and after purging with nitrogen, the mixture was stirred at 100 ° C. for 1 hour. Then, gauge pressure 1.2k with nitrogen
gf / cm ² (219 kPa) to a reaction temperature of 10
0 ° C., the maximum pressure during the reaction is 5 kgf / cm ² (490 k
Under the condition of Pa), 2.5 mol of ethylene oxide was reacted with 1 equivalent of the amino group of o-tolylenediamine. When the internal pressure of the autoclave stops changing,
100 ° C., 10 mmHgabs. (1330 Pa), and a reduced pressure treatment was performed for 30 minutes. After pressurizing to an atmospheric pressure with nitrogen, 0.05 mol of potassium hydroxide (in the form of a 50% by weight aqueous solution of potassium hydroxide) is added to 1 mol of o-tolylenediamine, and 10 mol of the mixture is stirred.
0 ° C., 10 mmHgabs. (1330 Pa) Dehydration under reduced pressure was performed for 3 hours under the following conditions. Then, at the same temperature, 20 mmHgabs. The addition reaction of propylene oxide was performed from a reduced pressure of (2660 Pa) until the OHV became 350 mgKOH / g. The maximum reaction pressure at this time was 4 kgf / cm ² (392 kPa). When the internal pressure change of the autoclave disappeared, 100 ° C,
10 mmHgabs. (1330 Pa) under reduced pressure for 2 hours to obtain a crude polyol. After pressurizing to atmospheric pressure with nitrogen, 1 mol of oxalic acid aqueous solution (in the form of 9 wt% oxalic acid aqueous solution) is added to 1 mol of potassium in the crude polyol, and neutralization reaction is carried out at 80 ° C. for 2 hours. went. Then, t-butylhydroxytoluene (BH) as an antioxidant was added to 100 parts by weight of the crude polyol.
T) and 8000 ppm of adsorbent KW-700 (manufactured by Kyowa Chemical Industry Co., Ltd.), and finally 105 ° C., 10 mmHgabs.
(1330 Pa), a pressure reduction treatment was performed for 3 hours.
Then, the mixture was filtered under reduced pressure using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyol. The hydroxyl value of the polyol after the purification treatment is 358 mgK
OH / g.

Comparative Example 2 Polyol C A 1-liter pressure-resistant autoclave equipped with a stirrer, a pressure gauge, an alkylene oxide injection port and a nitrogen inlet was charged with MDA-220 (manufactured by Mitsui Toatsu Chemicals, Inc .: 4,
0.25 mol of triethanolamine (manufactured by Mitsui Toatsu Chemicals, Inc.) is added to 1 mol of 4'-diaminodiphenylmethane (trade name of 4'-diaminodiphenylmethane). 8 for parts
4.2% by weight), and after purging with nitrogen, the mixture was stirred at 100 ° C. for 1 hour. Then, gauge pressure 1.2k with nitrogen
gf / cm ² (219 kPa) to a reaction temperature of 10
0 ° C., the maximum pressure during the reaction is 5 kgf / cm ² (490 k
Under the condition of Pa), 2.5 mol of ethylene oxide was reacted with 1 equivalent of the amino group of 4,4′-diaminodiphenylmethane. When the change in the internal pressure of the autoclave has ceased, 100 ° C., 10 mmHgabs. (133
(0 Pa) under reduced pressure for 30 minutes. After pressurizing to atmospheric pressure with nitrogen, 0.05 mol of potassium hydroxide (in the form of a 50% by weight aqueous potassium hydroxide solution) is added to 1 mol of 4,4'-diaminodiphenylmethane, and the mixture is stirred. , 100 ° C, 10mmHgab
s. (1330 Pa) Dehydration under reduced pressure was performed for 3 hours under the following conditions. Then, at the same temperature, 20 mmHgabs.
OHV is 350mgK from the reduced pressure of (2660Pa)
The addition reaction of propylene oxide was performed until OH / g was reached. The maximum reaction pressure at this time was 4 kgf / cm ² (3
92 kPa). When the change in the internal pressure of the autoclave has ceased, 100 ° C., 10 mmHgabs. (1
Under reduced pressure treatment for 2 hours under the condition of 330 Pa), a crude polyol was obtained. After pressurizing to atmospheric pressure with nitrogen,
1 mol of oxalic acid aqueous solution (in the form of 9% by weight oxalic acid aqueous solution) was added to 1 mol of potassium in the crude polyol, and 8 mol of oxalic acid aqueous solution was added.
A neutralization reaction was performed at 0 ° C. for 2 hours. Thereafter, 800 ppm of t-butylhydroxytoluene (BHT) as an antioxidant and 8000 pp of an adsorbent KW-700 (manufactured by Kyowa Chemical Co., Ltd.) were added to 100 parts by weight of the crude polyol.
m, and while gradually performing dehydration under reduced pressure,
° C, 10 mmHgabs. (1330 Pa)
A reduced pressure treatment was performed for a time. Then, the mixture was filtered under reduced pressure using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyol. The hydroxyl value of the polyol after the purification treatment was 357 mgKOH / g.

For the purpose of clarifying the effects of the polyol obtained in the examples, a rigid polyurethane foam was produced. Raw materials, abbreviations, and analytical methods used in Examples and Comparative Examples are described below. (Polyols A to C); Example 2 (Polyol A) and Comparative Example 3 (Polyol B), Comparative Example 4 (Polyol C) (Polyol D); Polyoxyalkylene polyol HS-350 manufactured by Mitsui Toatsu Chemicals, Inc. . Hydroxyl value 350mg
KOH / g (polyol E); a polyoxyalkylene polyol SU-450 manufactured by Mitsui Toatsu Chemicals, Inc. Hydroxyl value 450mg
KOH / g (catalyst) 1; an amine catalyst manufactured by Kao Corporation. N, N, N ', N'-tetramethylhexamethylenediamine (foam stabilizer) L-5420; Nippon Unicar Co., Ltd. silicone foam stabilizer (flame retardant) TCPP; Daihachi Chemical Co., Ltd. phosphorus compound .
Tris (2-chloropropyl) phosphate (foaming agent) water; using ion-exchanged water (isocyanate) Cosmonate M-200; a polyisocyanate compound manufactured by Mitsui Toatsu Chemicals, Inc. Polymeric MDI NCO% 31.3 Physical properties of rigid polyurethane foam; density, compressive strength,
The low-temperature dimensional stability (the dimensional change of the foam after standing at −30 ° C. for 24 hours) was determined by the method of JIS K 7220. Further, measurement of dimensional stability under wet heat (dimensional change rate of the foam after standing at 70 ° C. and a relative humidity of 95% for 24 hours) and after demolding the foam (after 5 minutes from demolding)
Was observed. When the foam surface was in a good state without fragility (flyability), evaluation was made with ○. When there was a little fragility, it was evaluated with △, and when it was fragile, it was evaluated with x. Further, the closed cell ratio of the foam was measured according to the method described in ASTM D-2856.

After mixing the polyols (A, B, C) obtained in Examples and Comparative Examples with polyols D and E, 1, L-5420 and TCPP were stirred and mixed at the ratios shown in Table 1 to form a resin premix.
Adjusted to 2 ° C. The equivalent ratio (NCO index) between active hydrogen and isocyanate groups in the resin premix is 1.
The amount of Cosmonate M-200 that was adjusted to 05 was adjusted to 22 ° C. Next, the resin premix prepared above and 5
Vigorous stirring and mixing for 200 seconds, immediately 200mm x 200mm
It was poured into a wooden box of 200 mm and foamed. The obtained rigid polyurethane foam was allowed to stand at 22 ° C. and a relative humidity of 40% for 24 hours. A sample having a size of 8 cm × 8 cm × 4 cm was cut out, the density was measured, and various physical properties were measured. The results are shown in Table 1. The composition of the resin premix in Table 1 indicates parts by weight of each component. The compressive strength of the foam was measured using a sample in the foam expansion direction.

[0060]

[Table 1]

[0061]

As can be seen from Table 1, the polyol (polyol A) using the methylene-crosslinked polyphenylenepolyamine containing triaminodiphenylmethanes as the main component of the present invention as an initiator.
Rigid polyurethane foams having excellent compressive strength, low temperature and wet heat dimensional stability as compared with foams using polyols having o-tolylenediamine (polyol B) or diphenylmethanediamine (polyol C) as an initiator. In addition, the closed cell ratio of the foam is high, and the foam surface condition is good.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naoki Sato 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Saku Izugawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] An alkylene oxide adduct of a methylene-bridged polyphenylenepolyamine containing triaminodiphenylmethane, which has a hydroxyl value of 10 to 700 mg KO.
H / g. 2. The method according to claim 2, wherein the triaminodiphenylmethane is 40 to 9%.
An active hydrogen compound containing 30 to 100% by weight of a methylene-crosslinked polyphenylene polyamine containing 9.9% by weight in the presence of a basic catalyst at a reaction temperature of 40 to 150 ° C and a maximum reaction pressure of 10
^{2. An} alkylene oxide addition polymerization is carried out under a condition of kgf / cm ² (980 kPa).
A method for producing the polyol as described above. 3. A method for producing a polyurethane resin, comprising reacting a polyol composition containing 2 to 100% by weight of the polyol according to claim 1 with a polyisocyanate compound.